This invention concerns a microbial process for production of compositions of matter containing isomers of jasmonic acid having the structure: ##STR5##
which are flavor acceptable as well as isomers having the structure: ##STR6##
which are also flavor acceptable. This invention is also concerned with the production of methyl jasmonate isomers from the aforementioned jasmonic acid isomers.
Considerable time and effort have been expended by microbiologists in the search for better processes for the production of jasmonic acid and methyl jasmonate which are flavor acceptable isomers, including those isomers defined according to the structure: ##STR7##
wherein R is methyl or hydrogen. Thus, Broadbent in United Kingdom Patent Specification No. 1,286,266 published on Aug. 23, 1972 discloses and claims a process for the manufacture of jasmonic acid which comprises cultivation of the organism Lasiodiplodia theobromae in a nutrient medium containing an assimilable source of carbon and an assimilable source of nitrogen followed by isolation of the product from the culture medium. Gunther, et al, German Democratic Republic Patent DD 279 688 published on Jun. 13, 1990 discloses a process for the production of 7-iso-jasmonic acid by strains of the organism Botryodiplodia theobromae in aerobic culture. This work is also discussed in the paper Miersch, et al, Phytochemistry, Volume 26, No. 4, pages 1037-1039, 1987, entitled "(+)-7-ISO-JASMONIC ACID AND RELATED COMPOUNDS FROM BOTRYODIPLODIA THEOBROAME." The organisms, Botryodiplodia theobromae and Lasiodermea theobromae are synonyms of Diplodia gossypina as discussed in the paper Jones, MYCOTAXON, Volume VI, No. 1 at pages 24-26, July-September 1997 (title: "THE CURRENT TAXONOMIC STATUS OF DIPLODIA GOSSYPINA." As confirmed by Hausler and Munch in the article entitled "Microbial Production of Natural Flavors," Volume 63, No. 10, ASM News at pages 551-559:
"Another plant fatty acid metabolite, jasmonic acid, an endogenous plant growth regulator with a variety of physiological functions, is produced by means of a similar metabolic pathway. After a lipoxygenase produces a hydroperoxide derivative of linolenic acid, this compound is converted to its allene oxide, which cyclizes. .beta.-Oxidation and double-bond reduction yields jasmonic acid. The methylester of jasmonic acid is not only a volatile plant hormone, possibly involved in interplant communication, but is also an important flavor and fragrance molecule that imparts a sweet-floral, jasmine-like note . . . PA1 Otto Miersch and his collaborators at the Institute of Plant Biochemistry, Halle-Saale, Germany, who were studying fungal plant pathogens, including Botryodiplodia theobromae, discovered that such microorganisms produce jasmonic acid. The biosynthetic steps leading to jasmonic acid in this filamentous fungus are probably similar to those found in plants. Recently our laboratory, which is evaluating this strain's capacity for producing jasmonic acid, found that B. theobromae yields only very low concentrations of jasmonic acid in liquid culture. Such findings suggest that the biosynthesis and excretion of jasmonic acid is strictly controlled during the growth cycle of this fungus on plants in its natural habitat."no bioprocesses for the high yield production of fruit flavor-acceptable jasmonic acid or methyl jasmonate exist. The Hausler and Munch paper was published in October 1997. ASM News is published by the American Society for Microbiology. PA1 (i) Diplodia gossypina ATCC 10936; PA1 (ii) Diplodia gossypina ATCC 20575; PA1 (iii) Diplodia gossypina NRRL 25011; and PA1 (iv) Diplodia gossypina ATCC 36037 PA1 (i) Diplodia gossypina ATCC 10936; PA1 (ii) Diplodia gossypina ATCC 20575; PA1 (iii) Diplodia gossypina NRRL 25011; and PA1 (iv) Diplodia gossypina ATCC 36037. PA1 (i) Diplodia gossypina ATCC 10936; PA1 (ii) Diplodia gossypina ATCC 20575; PA1 (iii) Diplodia gossypina NRRL 25011; or PA1 (iv) Diplodia gossypina ATCC 36037 PA1 (a) extraction of the jasmonic acid from the fermentation broth with an extraction solvent such as ethyl acetate to form ajasmonic acid extract; PA1 (b) concentration of the jasmonic acid extract whereby the extraction solvent is stripped; PA1 (c) esterification of the resulting jasmonic acid with methyl alcohol whereby the methyl jasmonate is formed according to one of the reactions: ##STR25## PA1 (d) concentration of the resulting methyl jasmonate. PA1 anise oil; PA1 ethyl-2-methyl butyrate; PA1 vanillin; PA1 cis-3-heptenol; PA1 cis-3-hexenol; PA1 trans-2-heptenal; PA1 butyl valerate; PA1 2,3-diethyl pyrazine; PA1 methyl cyclopentenolone; PA1 benzaldehyde; PA1 valerian oil; PA1 3,4-dimethoxyphenol; PA1 amyl acetate; PA1 amyl cinnamate; PA1 .gamma.-butyryl lactone; PA1 furfural; PA1 trimethyl pyrazine; PA1 phenyl acetic acid; PA1 isovaleraldehyde; PA1 ethyl maltol; PA1 ethyl vanilin; PA1 ethyl valerate; PA1 ethyl butyrate; PA1 cocoa extract; PA1 coffee extract; PA1 peppermint oil; PA1 spearmint oil; PA1 clove oil; PA1 anethol; PA1 cardamom oil; PA1 wintergreen oil; PA1 cinnamic aldehyde; PA1 ethyl-2-methyl valerate; PA1 .gamma.-hexenyl lactone; PA1 2,4-decadienal; PA1 2,4-heptadienal; PA1 methyl thiazole alcohol (4-methyl-5-.beta.-hydroxyehtyl thiazole); PA1 2-methyl butanethiol; PA1 4-mercapto-2-butanone; PA1 3-mercapto-2-pentanone; PA1 1-mercapto-2-propane; PA1 benzaldehyde; PA1 furfural; PA1 furfuryl alcohol; PA1 2-mercapto propionic acid; PA1 alkyl pyrazine; PA1 methyl pyrazine; PA1 2-ethyl-3-methyl pyrazine; PA1 tetramethyl pyrazine; PA1 polysulfides; PA1 dipropyl disulfide; PA1 methyl benzyl disulfide; PA1 alkyl thiophene; PA1 2,3-dimethyl thiophene; PA1 5-methyl furfural; PA1 acetyl furan; PA1 2,4-decadienal; PA1 guiacol; PA1 phenyl acetaldehyde; PA1 .beta.-decalactone; PA1 d-limonene; PA1 acetoin; PA1 amyl acetate; PA1 maltol; PA1 ethyl butyrate; PA1 levulinic acid; PA1 piperonal; PA1 ethyl acetate; PA1 n-octanal; PA1 n-pentanal; PA1 n-hexanal; PA1 diacetyl; PA1 monosodium gulatamate; PA1 monopotassium glutamate; PA1 sulfur-containing amino acids, e.g., cysteine; PA1 hydrolyzed vegetable protein; PA1 2-methylfuran-3-thiol; PA1 2-methyldihydrofuran-3-thiol; PA1 2,5-dimethylfuran-3-thiol; PA1 2 hydrolyzed fish protein; PA1 tetramethyl pyrazine; PA1 propylpropenyl disulfide; PA1 propylpropenyl trisulfide; PA1 diallyl disulfide; PA1 diallyl trisulfide; PA1 dipropenyl disulfide; PA1 dipropenyl trisulfide; PA1 4-methyl-2-[(methylthio)-ethyl]-1,3-dithiolane; PA1 4,5-dimetyl-2-(methylthiomethyl)-1,3-dithiolne; and PA1 4-methyl-2-(methylthiomethyl)-1,3-dithiolane. PA1 .beta.-Ethyl-cinnamaldehyde; PA1 Eugenol; PA1 Dipentene; PA1 .beta.-Damascenone; PA1 Maltol; PA1 Ethyl maltol; PA1 Delta-Undecalactone; PA1 Delta-Decalactone; PA1 Benzaldehyde; PA1 Amyl acetate; PA1 Ethyl butyrate; PA1 Ethyl valerate; PA1 Ethyl acetate; PA1 2-Hexenol-1; PA1 2-Methyl-5-isopropyl-1,3-nonadiene-8-one; PA1 2,6-Dimethyl-1,6-undecadiene-10-one; PA1 2-ethyl-5-isopropyl acetophenone; PA1 2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronnaphthalene; PA1 Dodcahydro-3a,6,6,9a-tetramethyl naphthol(2,1-b) furan; PA1 4-Hydroxy hexanoic acid, .gamma.-lactone; and PA1 Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No. 3,589,372 issued on Jun. 29, 1971. PA1 Celery seed oil; PA1 Coffee extract; PA1 Bergamot oil; PA1 Cocoa extract; PA1 Nutmeg oil; and PA1 Origanum oil.
Thus, in the flavor and fragrance art, a need has arisen for the development and efficient high yield production of naturally occurring jasmonic acid and methyl jasmonate, which have heretofore been found to be useful and necessary for the creation of flavor formulations used in augmenting or enhancing the aroma or taste of foodstuffs, chewing gums, toothpaste, medicinal products, chewing tobaccos and smoking tobaccos and also useful in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles (e.g., solid or liquid anionic, cationic, nonionic or zwitterionic detergents, perfumed polymers, fabric softener compositions, fabric softener articles, hair preparations, cosmetic powders and the like).
Methyl jasmonate (without indicating which isomer) is disclosed by Arctander, Perfume and Flavor Chemicals at monograph 2093 to have a "Powerful floral-herbaceous, sweet-tenacious odor representing typical background notes of Jasmin absolute." Arctander further discloses that this material "is an almost obvious candidate for work on improved artificial Jasmin absolute." Acree, et al, J. Agric. Food Chem., 1985, Volume 33, pages 425-427, discloses that the isomer of methyl jasmonate having the structure: ##STR8##
and having an optical rotation (.alpha..sub.D.sup.20) of +58 has a strong odor, whereas the other stereoisomers of (Z)-methyl jasmonate are substantially odorless.
No specific disclosures exist in the prior art showing the use of the jasmonic acid isomers of our invention defined according to the structure: ##STR9##
or defined according to the structure: ##STR10##
for use as flavor adjuvants (wherein R is methyl or hydrogen). Furthermore, nothing in the prior art discloses the stereoisomer of the compound having the structure: ##STR11##
particularly the stereoisomer having the optical rotation (.alpha..sub.D.sup.20) of +58.degree..